CN108597900B - Preparation method of graphene/phenylenediamine flexible composite membrane electrode - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 239000012528 membrane Substances 0.000 title claims abstract description 84
- 150000004986 phenylenediamines Chemical class 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004202 carbamide Substances 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 17
- 239000007772 electrode material Substances 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000010408 sweeping Methods 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention provides a preparation method of a graphene/phenylenediamine flexible composite membrane electrode, which comprises the following steps: 1) preparing a graphene oxide aqueous solution according to an improved Hummers method; 2) under the ultrasonic condition, uniformly mixing the graphene oxide aqueous solution and urea according to the mass ratio of 1:1-8:1-3.5 of the graphene oxide, the urea and the phenylenediamine; slowly dripping the phenylenediamine aqueous solution into the mixed solution to ensure that the concentration of the graphene oxide aqueous solution in the system reaches 2-7 mg/mL; pouring the mixture into a container for drying to obtain a graphene oxide/phenylenediamine/urea composite membrane; 3) and soaking the composite membrane in HI, washing and heating at low temperature to obtain the graphene/phenylenediamine flexible composite membrane electrode. According to the invention, urea and graphene oxide are ultrasonically and uniformly mixed, so that agglomeration and stacking of the graphene oxide caused by the fact that the graphene oxide is solidified under the induction of phenylenediamine molecules in a short time can be effectively avoided, and the capacitance performance of the flexible composite membrane electrode can be effectively enhanced.
Description
Technical Field
The invention relates to preparation of a membrane electrode material, in particular to a preparation method of a graphene/phenylenediamine flexible composite membrane electrode.
Background
After the oil crisis in the 70 th 20 th century, energy shortage has become a great challenge for human society, and solving the problems of efficient utilization of energy and development of novel clean energy has become a major concern in the world today. In recent years, high-efficiency energy storage devices have attracted extensive attention of researchers. Electrochemical capacitors, also called supercapacitors, have the advantages of high energy storage efficiency, long service life, environmental friendliness, safety, reliability and the like, and have become a new type of energy storage element which is concerned with. In particular, as consumer electronics are being developed toward miniaturization, flexible, foldable, and wearable, the development of flexible, high power density and high energy density electrochemical capacitors has developed into an important direction for the research of energy storage devices. The electrode material has a crucial influence on the performance of the flexible electrochemical capacitor among the components constituting the electrochemical capacitor. Graphene is a monolayer of carbon atoms in sp2Two-dimensional crystals formed by hybridization have better mechanical and thermal conductivity and high specific surface area (the theoretical value is 2600 m)2g-1) High carrier mobility (2 xl 0)5cm2V-1s-1) And good flexibility [ Solid State Commm.,2008,146, 351-; science, 2008,321, 385-; nano Lett.,2008,8, 902-; chem. mater, 2008,20,6792-]And thus is considered to be an ideal flexible supercapacitor electrode material.
At present, a flexible graphene film electrode material [ Nano lett, 2012,12, 1806-; mate, 2009,21, 3007-; mate, 2012,24, 1089-; ACS Nano,2013,7, 4042-4049; adv.mater, 2013,25, 3985-.
It is a commonly adopted method of researchers to increase the pseudocapacitance and improve the material energy storage performance by introducing pseudocapacitance materials, such as phenylenediamine molecules, between graphene sheet layers to prevent the stacking of the graphene sheet layers [ Journal of materials Chemistry,2012,22, 18775-; J.Mater.chem.A,2013,1, 3454-3462; NanoEnergy 2015,17, 160-170; chemistry of Materials 2016,28,9110-9121. Although the specific capacitance of the composite material is obviously increased under low current density due to the introduction of the phenylenediamine molecules into the graphene, the capacitance performance of the phenylenediamine molecule functionalized graphene composite electrode material is far lower than the theoretical value. The main reason is that a small amount of phenylenediamine molecules are in contact with a graphene oxide solution of a graphene precursor, so that graphene oxide is easily solidified in a short time, the prepared graphene is agglomerated, and a close-packed structure is formed, so that on one hand, the full utilization of the effective specific surface area of the graphene is influenced, the transmission of electrolyte ions in an internal pore channel of a composite membrane electrode material is limited by diffusion dynamics, on the other hand, the effective compounding of phenylenediamine and graphene is influenced, and the capacitance performance reason of the prepared phenylenediamine composite flexible composite membrane electrode is lower than the theoretical value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the graphene/phenylenediamine flexible composite membrane electrode, which has the advantages of simple process, mild experimental conditions, low cost and batch preparation; the flexible composite membrane electrode prepared by the method is used as a super capacitor electrode material, and the capacitance performance of the flexible composite membrane electrode is obviously improved.
The invention provides a preparation method of a graphene/phenylenediamine flexible composite membrane electrode, which comprises the following steps:
the first step is as follows: preparing a graphene oxide aqueous solution by taking graphite as a raw material according to an improved Hummers method;
the second step is that: under the ultrasonic condition, uniformly mixing the graphene oxide aqueous solution and urea according to the mass ratio of 1:1-8:1-3.5 of the graphene oxide, the urea and the phenylenediamine; slowly dripping the phenylenediamine aqueous solution into the mixed solution to ensure that the concentration of the graphene oxide aqueous solution in the system reaches 2-7 mg/mL; and pouring the mixture into a polytetrafluoroethylene container to be dried at the temperature of 20-35 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane.
The mass ratio of the graphene oxide to the urea to the phenylenediamine is preferably 1:5: 2.3.
The third step: soaking the graphene oxide/phenylenediamine/urea composite membrane obtained in the second step in HI at room temperature overnight, then respectively washing the membrane by distilled water and absolute ethyl alcohol alternately for multiple times, and then heating the membrane at low temperature to prepare the graphene/phenylenediamine flexible composite membrane electrode.
Further:
in the second step, the phenylenediamine is o-phenylenediamine, m-phenylenediamine or p-phenylenediamine.
The drying treatment temperature in the second step is preferably 30 ℃.
In the second step, the polytetrafluoroethylene container can be replaced by a plastic container or a glass container.
The conditions of the low-temperature heating treatment in the third step are preferably as follows: heating at 150 ℃ and 175 ℃ for 1-3 hours, and further preferably at 165 ℃ for 1 hour.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, urea is combined with the graphene oxide aqueous solution, and then phenylenediamine molecules are added into the mixed solution, so that the condition that the phenylenediamine molecules are directly added into the graphene oxide solution to induce the graphene oxide solution to be solidified and stacked in a short time is effectively avoided, the dispersibility of easy mixing is improved, the phenylenediamine molecules are conveniently and uniformly inserted into graphene oxide lamella layers, the effective specific surface area of graphene is fully utilized, and the prepared graphene/phenylenediamine flexible composite membrane pore channel structure is convenient for electrolyte ion transfer, thereby improving the capacitance performance of the graphene/phenylenediamine flexible composite membrane.
2. In the invention, in the process of gradually drying the graphene oxide/phenylenediamine/urea composite membrane, precipitated urea microcrystals are used as porous templates, so that excessive shrinkage of the composite membrane in the drying process is avoided; on the other hand, the formed macroporous structure is convenient for storing the electrolyte, and the transmission distance of the electrolyte in the electrode material is shortened, so that the capacitance performance of the prepared graphene/phenylenediamine flexible composite membrane electrode is improved.
3. The experimental condition is mild, the heating treatment temperature is 150-.
Drawings
Fig. 1 is an electronic photograph of a graphene/phenylenediamine flexible composite membrane electrode a prepared in example 1.
Fig. 2 is scanning electron microscope images of graphene/phenylenediamine flexible composite membrane electrodes a, (a) and b (b) prepared in embodiment 1, and the insets are scanning electron microscope images of the hole walls thereof at magnifications respectively.
FIG. 3 shows that the graphene/phenylenediamine flexible composite membrane electrode prepared in embodiment 2 is 1M H2SO4And in the electrolyte, the mass ratio capacitance values under different sweeping speeds.
FIG. 4 shows that the graphene/phenylenediamine flexible composite membrane electrode prepared in embodiment 3 is 1M H2SO4In the electrolyte, the current density is 0.5Ag-1Charge and discharge curves at time.
Fig. 5 is a scanning electron microscope image of the graphene/phenylenediamine flexible composite membrane electrode prepared in example 4.
FIG. 6 shows that the graphene/phenylenediamine flexible composite membrane electrode prepared in example 6 is at 1M H2SO4Specific capacitance values at different sweep rates in the electrolyte.
FIG. 7 shows that the thickness of the graphene/phenylenediamine flexible composite membrane electrode prepared in example 7 is 1mV s-1Cyclic voltammetry curve of (a).
Detailed Description
Example 1 preparation of graphene/phenylenediamine flexible composite membrane electrode
Preparing a graphene oxide/phenylenediamine/urea composite membrane: according to a modified Hummers method, graphite is used as a raw material, and a graphene oxide aqueous solution with the concentration of 3mg/mL is prepared. Firstly, 1mL of 3mg/mL graphene oxide aqueous solution and 15mg urea aqueous solution are ultrasonically homogenized. And then, slowly dripping 0.44ml of 16.0mg/ml p-phenylenediamine aqueous solution into the mixed solution, uniformly mixing by ultrasound, pouring into a polytetrafluoroethylene cover with the diameter of 2.8cm, and drying at 30 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane a.
For comparison, 0.44mL of 16.0mg/mL p-phenylenediamine aqueous solution is directly and slowly dropped into 1mL of 3mg/mL graphene oxide aqueous solution for ultrasonic mixing, and the mixture is poured into a polytetrafluoroethylene cover with the diameter of 2.8cm and dried at 30 ℃ to obtain the graphene oxide/phenylenediamine composite membrane b.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: and respectively soaking the composite films a and b in HI at room temperature overnight, respectively washing the composite films a and b with distilled water and absolute ethyl alcohol alternately for multiple times, heating the composite films at 165 ℃ for 1 hour, removing impurities, and respectively preparing graphene/phenylenediamine flexible composite film electrodes a and b.
Fig. 1 is an electronic photograph of the prepared graphene/phenylenediamine flexible composite membrane electrode a. The flexibility is very good as shown in the figure; fig. 2 is a scanning electron microscope image of the prepared graphene/phenylenediamine flexible composite membrane electrodes a and b. It can be seen from the figure that, compared with the graphene/phenylenediamine flexible composite membrane electrode b, the graphene/phenylenediamine flexible composite membrane electrode a has more uniform holes distributed on the surface, thinner pore walls and obvious folds and multi-layer distribution (a in fig. 2), because the urea formed in the gradual drying process of the composite membrane is crystallized into ureaAnd a macroporous structure formed by the template. In addition, the addition of urea effectively avoids the short-time induction of graphene oxide agglomeration and stacking by phenylenediamine, and therefore, the formed pore wall is thinner (an inset in fig. 2 a). Respectively using graphene/phenylenediamine flexible composite films a and b as electrode materials to assemble a symmetrical super capacitor, and adopting a two-electrode method to 1MH2SO4The capacitance performance of the electrolyte is tested in the electrolyte, and when the sweep speed is 1mV s-1The mass specific capacitance can reach 430F g-1And 384F g-1，Therefore, the capacitance performance of the graphene/phenylenediamine flexible composite membrane electrode material prepared by mixing urea and graphene oxide and then mixing the urea and phenylenediamine is obviously improved.
Example 2 preparation of graphene/phenylenediamine flexible composite membrane electrode
Preparing a graphene oxide/phenylenediamine/urea composite membrane: according to a modified Hummers method, graphite is used as a raw material, and a graphene oxide aqueous solution with the concentration of 3mg/mL is prepared. Firstly, 1mL of 3mg/mL graphene oxide aqueous solution and 10mg urea aqueous solution are ultrasonically homogenized. And then, slowly dripping 0.44ml of 16.0mg/ml p-phenylenediamine aqueous solution into the mixed solution, uniformly mixing by ultrasound, pouring into a polytetrafluoroethylene cover with the diameter of 2.8cm, and drying at 30 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: the same as in embodiment 1.
The prepared graphene/phenylenediamine flexible composite membrane is used as an electrode material to assemble a symmetrical super capacitor, and a two-electrode method is adopted at 1M H2SO4The capacitance performance of the electrolyte is tested, the specific capacitance value of the electrolyte is gradually reduced along with the increase of the scanning speed, and when the scanning speed is 1mV s-1When the mass specific capacitance reaches 410.5F g-1As shown in fig. 3.
Example 3 preparation of graphene/phenylenediamine flexible composite membrane electrode
Preparing a graphene oxide/phenylenediamine/urea composite membrane: according to a modified Hummers method, graphite is used as a raw material, and a graphene oxide aqueous solution with the concentration of 3mg/mL is prepared. Firstly, 1mL of 3mg/mL graphene oxide aqueous solution and 20mg of urea aqueous solution are ultrasonically homogenized. And then, slowly dripping 0.44ml of 16.0mg/ml p-phenylenediamine aqueous solution into the mixed solution, uniformly mixing by ultrasound, pouring into a polytetrafluoroethylene cover with the diameter of 2.8cm, and drying at 30 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: the same as in embodiment 1. The prepared graphene/phenylenediamine flexible composite membrane is used as an electrode material to assemble a symmetrical super capacitor, and a two-electrode method is adopted at 1M H2SO4And testing the capacitance performance of the electrolyte. When the current density is 0.5A/g, the charge-discharge curve shows a symmetrical triangle, and the mass specific capacitance reaches 383.6F g-1As shown in fig. 4.
Example 4 preparation of graphene/phenylenediamine flexible composite membrane electrode
Preparing a graphene oxide/phenylenediamine/urea composite membrane: according to a modified Hummers method, graphite is used as a raw material, and a graphene oxide aqueous solution with the concentration of 3mg/mL is prepared. Firstly, 1mL of 3mg/mL graphene oxide aqueous solution and 25mg urea aqueous solution are ultrasonically homogenized. And then, slowly dripping 0.44ml of 16.0mg/ml p-phenylenediamine aqueous solution into the mixed solution, uniformly mixing by ultrasound, pouring into a polytetrafluoroethylene cover with the diameter of 2.8cm, and drying at 30 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane a.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: the same as in embodiment 1.
Fig. 5 is a scanning electron microscope image of the prepared graphene/phenylenediamine flexible composite membrane electrode. As can be seen from the figure, the surface of the material has a large number of holes formed by urea crystals as templates, and the hole walls of the material are provided with a large number of folds.
Example 5 preparation of graphene film electrode material
Preparing a graphene oxide/phenylenediamine/urea composite membrane: the same as in embodiment 1.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: soaking the graphene oxide/phenylenediamine/urea composite membrane in HI at room temperature overnight, washing with distilled water and anhydrous ethanol alternately for multiple times, heating at 165 deg.C for 2 hr, and removingAnd impurities are removed, and the graphene/phenylenediamine flexible composite membrane electrode is prepared. Using a two-electrode approach at 1M H2SO4In the electrolyte, the electrolyte is used as an electrode material to assemble a symmetrical super capacitor, and when the scanning speed is 1mV s-1When the mass specific capacitance reaches 373.8F g-1。
Example 6 preparation of graphene/phenylenediamine flexible composite membrane electrode
Preparing a graphene oxide/phenylenediamine/urea composite membrane: according to a modified Hummers method, graphite is used as a raw material, and a graphene oxide aqueous solution with the concentration of 3mg/mL is prepared. Firstly, 1mL of 3mg/mL graphene oxide aqueous solution and 15mg urea aqueous solution are ultrasonically homogenized. And then, slowly dripping 0.44ml of 16.0mg/ml o-phenylenediamine aqueous solution into the mixed solution, uniformly mixing by ultrasound, pouring into a polytetrafluoroethylene cover with the diameter of 2.8cm, and drying at 30 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: the same as in embodiment 1. The prepared graphene/phenylenediamine flexible composite membrane electrode is used as an electrode material to assemble a symmetrical super capacitor, and a two-electrode method is adopted at 1M H2SO4The capacitance performance of the electrolyte is tested in the electrolyte, and when the sweep speed is 1mV s-1When the mass specific capacitance reaches 304F g-1As shown in fig. 6.
Example 7 preparation of graphene/phenylenediamine Flexible composite Membrane electrode
Preparing a graphene oxide/phenylenediamine/urea composite membrane: according to a modified Hummers method, graphite is used as a raw material, and a graphene oxide aqueous solution with the concentration of 10mg/mL is prepared. Firstly, 1mL of a 10mg/mL graphene oxide aqueous solution and 15mg of a urea aqueous solution are ultrasonically homogenized. And then, slowly dripping 0.44ml of 16.0mg/ml p-phenylenediamine aqueous solution into the mixed solution, uniformly mixing by ultrasound, pouring into a polytetrafluoroethylene cover with the diameter of 2.8cm, and drying at 30 ℃ to obtain the graphene oxide/phenylenediamine/urea composite membrane.
Preparing a graphene/phenylenediamine flexible composite membrane electrode: the same as in embodiment 1. The prepared graphene/phenylenediamine flexible composite membrane is used as an electrode material to assemble a symmetrical super capacitor, and a two-electrode method is adopted at 1M H2SO4And testing the capacitance performance of the electrolyte. FIG. 7 shows that the prepared graphene/phenylenediamine flexible composite membrane electrode is at 1mV s-1At the scanning speed, the mass specific capacitance of the cyclic voltammogram can reach 374F g-1Thus, the capacitor has better capacitance performance.
Claims (6)
1. A preparation method of a graphene/phenylenediamine flexible composite membrane electrode is characterized by comprising the following steps:
the first step is as follows: preparing a graphene oxide aqueous solution by taking graphite as a raw material according to an improved Hummers method;
the second step is that: under the ultrasonic condition, uniformly mixing the graphene oxide aqueous solution and urea according to the mass ratio of 1:1-8:1-3.5 of the graphene oxide, the urea and the phenylenediamine; slowly dripping the phenylenediamine aqueous solution into the mixed solution to ensure that the concentration of the graphene oxide aqueous solution in the system reaches 2-7 mg/mL; pouring the mixture into a polytetrafluoroethylene container, and drying the mixture at 20-35 ℃ to obtain a graphene oxide/phenylenediamine/urea composite membrane;
the third step: soaking the graphene oxide/phenylenediamine/urea composite membrane obtained in the second step in HI at room temperature overnight, then respectively washing the graphene oxide/phenylenediamine/urea composite membrane with distilled water and absolute ethyl alcohol alternately for multiple times, and then heating the membrane at low temperature to prepare a graphene/phenylenediamine flexible composite membrane electrode; the conditions of the low-temperature heat treatment are as follows: heating at 150-175 deg.C for 1-3 hr.
2. The method for preparing a graphene/phenylenediamine flexible composite membrane electrode according to claim 1, wherein in the second step, the phenylenediamine is o-phenylenediamine, m-phenylenediamine or p-phenylenediamine.
3. The method for preparing a graphene/phenylenediamine flexible composite membrane electrode according to claim 1, wherein the drying temperature in the second step is 30 ℃.
4. The method for preparing a graphene/phenylenediamine flexible composite membrane electrode according to claim 1, wherein in the second step, the polytetrafluoroethylene container is replaced by a glass container.
5. The method for preparing the graphene/phenylenediamine flexible composite membrane electrode according to claim 1, wherein in the second step, the mass ratio of the graphene oxide to the urea to the phenylenediamine is 1:5: 2.3.
6. The graphene/phenylenediamine flexible composite membrane electrode prepared by the method according to any one of claims 1 to 5.
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